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Articles 1 - 7 of 7
Full-Text Articles in Physical Chemistry
Computational Investigation Of The Ionization Potential Of Lead Sulfide Quantum Dots, Jessica Beyer
Computational Investigation Of The Ionization Potential Of Lead Sulfide Quantum Dots, Jessica Beyer
Scripps Senior Theses
The purpose of this work was to determine the impact of quantum dot size on ionization potential and to determine how the presence of carbonyl-based ligands affect the ionization potential of lead sulfide quantum dot systems. Ionization potential (IP) is defined as the energy required to remove an electron from an atom, molecule, or material. IP helps scientists determine how reactive the material of interest is, which is crucial information when manufacturing nanomaterials. Accurate quantum chemical calculations of ionization potential are challenging due to the computational cost associated with the numerical solution of the Dyson equation. In this work, the …
Here, There, And Everywhere: Probing Ubiquitin-Cavitand Binding Via 15n-1h Hsqc, Julia Didziulis
Here, There, And Everywhere: Probing Ubiquitin-Cavitand Binding Via 15n-1h Hsqc, Julia Didziulis
Scripps Senior Theses
Ubiquitination and other post-translational modifications play a major role in the proliferation of many neurodegenerative diseases, developmental disorders, and cancers, and as such are subjects of recently increased biochemical interest. Expanding upon such research, this study confirmed a robust method of ubiquitin expression and purification, then used 15N-1H HSQC to analyze ubiquitin samples containing varying concentrations of a deep cavitand with affinity for lysine and arginine side chains. In the pure ubiquitin spectrum, arginine side chain chemical shifts were detected in the nitrogen 80-85 ppm range and lysine side chain signals were undetected. However, upon introduction of the cavitand, collection …
Using Powder Diffraction To Give Insight Into Structures Of Ir2(Diisocyanomenthane)4x2 [Dimen] (X = Cl; Pf6; Bph4), Mairead Brownell
Using Powder Diffraction To Give Insight Into Structures Of Ir2(Diisocyanomenthane)4x2 [Dimen] (X = Cl; Pf6; Bph4), Mairead Brownell
Scripps Senior Theses
Ir2(dimen)42+ (dimen = 1,8-diisocyanomenthane) has been studied extensively as model compound to better understand catalysis of photochemical reactions. Although Ir2(dimen)42+ has been used primarily to observe the photophysical changes of metal-metal transitions, it gives great insight into the transitions that allow other d8-d8 metal complexes to undergo photochemical processes and generate hydrogen gas. The large visible range by which Ir2(dimen)42+ (1) can be electronically excited in solution is indicative of its two solution phase ground states, which interestingly have been hypothesized to resemble two unique packing structures observed in the powder state. In this study, the powder diffraction patterns of …
Reduced Electronic Spaces For Modeling Donor/Acceptor Interactions, Robert J. Cave, Stephen T. Edwards '06, John A, Kouzelos '07, Marshall D. Newton
Reduced Electronic Spaces For Modeling Donor/Acceptor Interactions, Robert J. Cave, Stephen T. Edwards '06, John A, Kouzelos '07, Marshall D. Newton
All HMC Faculty Publications and Research
Diabatic states for donor (D) and acceptor (A) interactions in electron transfer (ET) processes are formulated and evaluated, along with coupling elements (HDA) and effective D/A separation distances (rDA), for reduced electronic spaces of variable size, using the generalized Mulliken Hush model (GMH), applicable to an arbitrary state space and nuclear configuration, and encompassing Robin−Day class III and as well as class II situations. Once the electronic state space is selected (a set of n ≥ 2 adiabatic states approximated by an orbital space based on an effective 1-electron (1-e) Hamiltonian), the charge-localized GMH …
Tunneling Through Weak Interactions: Comparison Of Through-Space-, H-Bond-, And Through-Bond-Mediated Tunneling, Westin Kurlancheek '03, Robert J. Cave
Tunneling Through Weak Interactions: Comparison Of Through-Space-, H-Bond-, And Through-Bond-Mediated Tunneling, Westin Kurlancheek '03, Robert J. Cave
All HMC Faculty Publications and Research
Results from ab initio electronic structure theory calculations on model systems allow for the detailed comparison of tunneling through covalently bonded contacts, hydrogen bonds, and van der Waals contacts. Considerable geometrical sensitivity as well as an exponential distance dependence of the tunneling is observed for tunneling through various nonbonded contacts. However, the fundamental result from the present study is that at most a modest difference is observed between tunneling mediated by H-bonds and tunneling mediated by van der Waals contacts at typical distances for each type of interaction. These results are considered in relation to the pathways model of Beratan …
Article Are Hydrogen Bonds Unique Among Weak Interactions In Their Ability To Mediate Electronic Coupling?, Emily Cukier '03, Sarah Daniels '02, Eric Vinson '01, Robert J. Cave
Article Are Hydrogen Bonds Unique Among Weak Interactions In Their Ability To Mediate Electronic Coupling?, Emily Cukier '03, Sarah Daniels '02, Eric Vinson '01, Robert J. Cave
All HMC Faculty Publications and Research
Superexchange effects on the electronic coupling element for electron transfer are investigated using water dimers and atomic donors and acceptors. We compare the electronic coupling elements obtained with H-bonded dimers to those obtained for other water dimer geometries at given donor−acceptor and oxygen−oxygen distances. The H-bonded orientation does not yield significantly different coupling elements from non-H-bonded orientations at a given oxygen−oxygen distance. In addition, the distance dependence of the coupling mediated by H-bonds is not significantly different from that for other dimer geometries. It is found that protonation of the intervening waters has a significant effect on coupling elements for …
Chemical Applications Of Scanning Tunneling Microscopy, Paul West, John Kramer, David V. Baxter, Robert J. Cave, John D. Baldeschwieler
Chemical Applications Of Scanning Tunneling Microscopy, Paul West, John Kramer, David V. Baxter, Robert J. Cave, John D. Baldeschwieler
All HMC Faculty Publications and Research
The development of a scanning tunneling microscope at the California Institute of Technology is well under way. Electron tunneling has been demonstrated, and preliminary surface images of gold films have been obtained. Additional instrumental development is required to achieve the atomic resolution which is required for the study of chemical processes on surfaces. A theoretical model is also being developed for the study of tunneling of electrons from the probe to surfaces with molecular species absorbed, and with atomic and molecular species intervening between the probe and the surface. These experimental tools and theoretical models, which are being developed concurrently, …